Acyloxyvinyl alkyl sulfones and polymers thereof



Patented May 9, 1950 ACYLOXYVINYL SULFONES AND POLYMERS THEREOF JosephB. Dickey and Barry W. Coover, J r., Rochester, N. Y., assignora toEastman Kodak Company, Rochester, N. Y., a corporation of New Jersey NoDrawing. Application December 29, 1948, Serial No. 68,055

12 Claims. (Cl. 260-793) 1 This invention relates to vinyl alkylsulfones which are substituted in the vinyl group .with an acyloxygroup, polymers thereof, and to methods for preparing the. same.

The new compounds of our invention may be represented by the generalformula:

wherein R represents an alkyl group of the series CnH2n+l (e. g. methyl,ethyl, propyl, butyl, amyl, dodecyl, etc), an aryl group (e. g. phenyl)an aralkyl group (e. g. benzyl) and R1 and R2 each represents an alkylgroup of the series cnH2n+l as defined above and a phenyl group.

The compounds of the invention are valuable intermediates for thepreparation of other useful organic compounds. They are alsopolymerizable alone or .conjointly with other unsaturated organiccompounds to resinous polymers which are useful for the preparation ofwaterproofing compositions, films, sheets, fibers, and the like. Theycan also be molded and worked mechanically to the finished form by theusual methods of milling, sawing, boring, etc.

In accordance with the invention the new aeyloxy vinyl alkyl sulfonesmay be prepared by treating the desired vinyl alkyl sulfone withhypochlorous acid to obtain a mixture of achloro-fi-hydroxyethyl alkylsulfone and a-hydroxy-fi-chloroethyl alkyl sulfone, acylating themixture with an organic acid anhydride or an organic acid halide toobtain a mixed product of a-chloro-fl-acyloxyethyl alkylsulfone and o.-acyloxy-fi-chloroethyl alkyl sulfone, separating the individual productsfrom one another by fractional distillation under reduced pressure, andthen dehydrohalogenating the isolated (acyloxy-chloro-) ethyl alkylsulfones by heating with an organic base such as quinoline, pyridine,triethylamine, tributylamine, etc., to obtain the respective acyloxyvinyl alkyl sulfones in good yield. The vinyl alkyl sulfone startingmaterials can be prepared by known methods such as described in BritishPatent No. 442,524. The organic acid anhydride can be acetic anhydride,propionic anhydride, butyric anhydride, isobutyric anhydride, valericanhydride, lauric anhydride, stearic anhydride, etc. The organic acidhalide' can be acetyl chloride, propionyl chloride, butyryl chloride,isobutyryl chloride, valeryl chloride, lauroyl chloride, stearylchloride, etc. Further details of the process for obtaining the newcompounds of the invention are given in the examples.

The polymerization of the new acyloxyvinyl alkyl sulfones of ourinvention alone or conjointly with one or more other unsaturatedcompounds is accelerated by heat and by polymerization of vinyl andother unsaturated organic compounds. Exemplary of such catalysts are theorganic peroxides (e. g. benzoyl peroxide, acetyl peroxide, lauroylperoxide, etc), hydrogen peroxide, perborates (e. g. alkali metalperborates), persulfates (e. g. alkali metal persulfates) and ionicpolymerization catalysts (e. g. boron trifluoride). The polymerizationcan be effected in mass or in the presence of an inert diluent (e. g.water, acetic acid, lA-dioxane, acetonitrile, etc.). However, themonomers can also be emulsified in a liquid in which they are insoluble(e. g. in water) and the emulsion then subjected to polymerization. Themonomers can also be suspended in water using a relatively poordispersing agent (e. g. starch) and polymerized in granular form. Themonomers can also be polymerized as above described with one or morecopolymerizable unsaturated organic compounds, for example, with vinylcompounds (1. e. compounds containing the basic CH2=C group) such asvinyl acetate, vinyl propionate, vinyl butyrate, vinyl propionate, vinylbutyrate, vinyl trifluoroacetate, methyl acrylate, methyl methacrylate,styrene, ortho-acetamino styrene, amethylstyrene, 2,4 dichloro amethylstyrene. acrylonitrile, a. methacrylonitrile, aacetoxyacrylonitrile, a-acetoxy methacrylate, vinyl chloride, vinylfluoride, vinylidene dichloride, vinylidene chloride-fluoride, vinylmethylketone, trifluoromethyl vinylketone, vinylmethylether,vinylw-trifiuoroethyl ether, vinylmethylsulfone, vinyl sulfonamide,trans-p-cyanoand carboxamidomethyl acrylate, vinylmethylurethane,acrylamide, acrylic acid ethylamide, vinyl phthalimide, vinylsuccinimide, acrylic acid, vinyl naphthalene, isobutylene, ethylene,butadiene, a-acetoxybutadiene-L3, and with other unsaturated organiccompounds such as maleic anhydride, methyl maleate, methyl fumarate, andthe like.

The copolyrners of the invention may contain variable amounts of eachcommoner and are obtained with starting polymerization mixtures havingfrom 5 to molecular proportions of the new unsaturates and from 95 to 5molecular proportions of the above-mentioned other un-- saturatedorganic compounds. However, the preferred copolymers contain from to 90molecular proportions of the new acetoxyvinyl alicyl sulfones and from90 to 10 molecular proportions of the other unsaturated comonomersalthough in the case of copolymers with acrylonitrile and substitutedacrylonitriles, the best ratios are from 5 to 40 molecular proportionsof the e-acyloxyvinyl alkyl sulfones to from 95 to 60 molecularproportions of the acrylonitrile compound. The temperature ofpolymerization at normal pressures may be varied from 30 C. to 120 C.,preferably from 30 to 75 C. although in cases where high pressure isemployed the temperature may be as high as 200 0., and where an ioniccatalyst such as boron trifluoride is employed the temperature may be aslow as -'75 C. and still give satisfactory resinous polymers. Where thepolymerization is carried out in an inert solvent medium such aspreviously mentioned, the concentration of the monomers to bepolymerized can be varied from 1 to per cent of the weight of thesolvent employed.

The following examples will serve to illustrate our new unsaturates,polymers thereof, and the 7 manner of preparing the same.

Example 1.-Preparatlon of a-hZIdTOIlIll-fi-ChlOTO- ethyl methyl sulfoneand a-chloro-p-hydrozythyl methyl sulfone (CECl-CHOH-SOzCHa) anda-hydroxy-p-chloroethyl methyl sulfone (CH20H-CHCl-SO2CH:)

amounting together to a yield of about 90 per cent of calculated.

Example 2.--Preparation of a-acetoxy-fl-chloroethyl methyl sulfone anda-OhlOTO-B-GCEtOZZlethyl methyl sulfone 127 grams of the crude mixtureof chlorohydroxyethyl methyl sulfones prepared as described in Example1, was heated on av steam bath for several hours with 200 grams ofacetic anhydride. When the reaction was complete, the acetic acid whichformed and the excess of acetic anhydride were removed by distillation.The

tube at C. for a period of 24 hours.

sure gave as a product a yield of about '10 per cent of purea-acetoxyvinyl methyl sulfone For the preparation of othera-acyloxyvinyl alkyl sulfones where the allryl group is ethyl, propyl,isopropyl, isobutyl, sec. butyl, tertiary butyl, etc., the correspondingvinyl alkyl sulfone is treated with hypochlorous acid, acylated, theaacetoxy-fl-chloroethyl methyl sulfone obtained is separated from themixture and dehydrohalogenated, following the general proceduresdescribed in the preceding examples. Thus, with acetic anhydride oracetyl chloride, there were obtained a-acetoxyvinyl ethyl sulfone,c-acetoxyvinyl propyl sulfone, a-acetoxyvinyl isopropyl sulfone,aacetoxyvinyl butyl sulfone, a-acetoxyvinyl isobutyl sulfone,e-acetoxyvinyl sec-butyl sulfone, a.- acetoxyvinyl tert. butyl sulfone,with propionlc anhydride or propionyl chloride as the acylating agent,a-propionoxyvinyl methyl sulfone, c-propionoxyvinyl ethyl sulfone,a-propionoxyvinyl propyl sulfone, a-Dl'ODiOIlOXYVlIlYl isopropylsulfone, a-propionoxyvinyl butyl sulfone, a-propionoxyvinyl isobutylsulfone, e-propionoxyvinyl sec.- butyl sulfone, a-propionoxyvinyl'tert.-butyl suifone, etc., with butyric anhydric or butyryl chloride asthe acylating agent, e-butyryloxyvinyi methyl sulfone, a-butyryloxyvinylethyl sulfone, a-butyryloxyvinyl propyl sulfone, a-butyryloxyvinylisopropyl sulfone, a-butyryloxyvinyl butyl sulfone, a-butyryloxyvinylisobutyl sulfone, a-blltyryloxyvinyl sec-butyl sulfone,a-blltYl'YlOXYViIlyl tert.-butyl sulfone, etc., and with lsobutyricanhydride or isobutyryl chloride as the acylating agent,a-isobutyryloxyvinyl methyl sulfone, a-iSOblltYlYlOXYViDYl ethylsulfone. a-isobutyryloxyvinyl propyl sulfone, a-isobutyryloxyvinylisopropyl sulfone, a-isobutyryloxyvinyl butyl sulfone,a-iSOblltYlYlOXYVlDYI isobutyl sulfone, a-isobutyryloxyvinyl sec-butylsulfone, a-iSOblltYlYlOXY- vinyl tert.-butyl sulfone, etc.

Example 4.--Poly-a-acet0:z:yvinyl methyl suljone 10 grams ofa-acetoxyvinyl methyl sulfone and 0.1 gram of benzoyl peroxide weresealed in a tube and heated at 80 C. for a period of 24 hours. At theend of this time, the sulfone compound had polymerized to a clear, hard,readily moldable polymer. Similar kinds of resinous polymers were alsoobtained by substituting for the aacetoxyvinyl methyl sulfone in theabove example an equivalent amount of a-acetoxyvinyl ethyl sulfone ora-propionoxyvinyl methyl sulfone.

Example 5.-Copolymer of a-acetomyvinyl methyl sulfone and methylmethacrylate A mixture of 5 grams of a-acetoxyvinyl methyl sulfone, 5grams of methyl methacrylate and 0.1 gram of benzoyl peroxide was heatedin a sealed At the end of this time, the material in the tube had allpolymerized to a clear, hard polymer.

residue was then subjected to fractional distiila- I tion under reducedpressure, the a-acetoxy-flchloroand a-chloro-p-acetoxyethyl methylsulfones being obtained as pure compounds.

Example 3.a-aceto:cyvlnyl methyl sulfone A mixture of 17 grams ofa-flOBtOXY-fl-OhlOl'O- ethyl methyl sulfone and 25 grams of freshlydistilled synthetic quinoline was heated at to C. for a period of 5 to 6hours. Fractionation of the reaction mixture under reduced press- Inplace of methyl methacrylate, there can be substituted 5 grams ofstyrene to give a similar clear, hard copolymer of a-acetoxyvlnyl methylsulfone and styrene.

Example 6.C'opolymer of e-acetomyvinyl ethyl sulfone and acrylom'trile Amixture of 8 grams of acrylonitrile, 2 grams of a-acetoxyvinyl ethylsulfone, 50 grams of acetonitrile and 0.2 grams of acetyl peroxide washeated at 60 C. for a period of 24 hours. The copolymer which formed asa precipitate in the solution 01' acetonitrile was filtered out anddried.

The yield of copolymer was soluble in dimethyl formamide, solutions ofwhich were spinnable' into tough fibers. In place of the a-acetoxyvinylethyl sulfone in the above example, there can be substituted 2 grams ofa-propionoxyvinyl methyl sulfone to give a similar resinous copolymerfrom which tough fibers can be prepared.

It will be understood that other equally valuable resinous copolymers ofany of our new sulfones with other vinyl compounds such as thosementioned can be prepared with facility by employingthe generalprocedures of the examples used for illustration.

What we claim and desire to secure by Letters Patent of the UnitedStates of America is:

1. A compound selected from the group consisting of an a-acyloxyvinylalkyl sulfone and a p-acyloxyvinyl alkyl sulfone, wherein each acyloxygroup is selected from those consisting of a saturated fatty acidacyloxy group containing from 1 to 18 carbon atoms and a benzoyloxygroup.

2. An a-acyloxyvinyl alkyl sulfone wherein the acyloxy group is asaturated fatty acid acyloxy group containing from 1 to 18 carbon atoms.

3. An a-acetoxyvinyl alkyl sulfone.

4. a-acetoxyvinyl methyl sulfone.

5. An u-propionoxy alkyl sulfone.

6. a-propionoxy methyl sulfone.

7. a-acetoxyvinyl ethyl sulfone.

8. A polymer of a compound selected from the group consisting oi ana-acyloxyvinyl alkyl sultone and a fi-acyloxyvinyl alkyl sulfone,wherein each acyloxy group is selected from those consisting of asaturated fatty acid acyloxy group containing from 1 to 18 carbon atomsand a benzoyloxy group.

9. A polymer of an a-acyloxyvinyl sulfone wherein the acyloxy group is asaturated fatty acid acyloxy group containing from 1 to 18 carbon atoms.

10. A copolymer of from 5 to 95 molecular proportions of a-acetoxyvinylmethyl sulfone and from 95 to 5 molecular proportions of methylmethacrylate.

11. A copolymer of from 5 to molecular proportions of a-acetoxyvinylethyl sulfone and from 95 to molecular proportions of acrylonitrile.

12. A copolymer of from 5 to 40 molecular proportions ofa-propionoxyvinyl methyl sulfone and from to 60 molecular proportions ofacrylo- 4 nitrile.

' JOSEPH B. DICKEY.

HARRY W. COOVER, JR.

REFERENCES CITED .9 Number UNITED STATES PATENTS Name Date 2,427,640Whitehill Sept. 16, 1947

8. A POLYMER OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF AN-ACYLOXYVINYL ALKYL SULFONE AND A B-ACYLOXYVINYL ALKYL SULFONE, WHEREINEACH ACYLOXY GROUP IS SELECTED FROM THOSE CONSISTING OF A SATURATEDFATTY ACID ACYLOXY GROUP CONTAINING FROM 1 TO 18 CARBON ATOMS AND ABENZOYLOXY GROUP.